Specimen molding



June 20, 1950 E. F. CHAMPAYGNE SPECIMEN MOLDING Filed Feb. 5, 1945 3 Sheets-Sheet 1 @www ATTORN EY June 20, 1950 Filed Feb. 3, 1945 E. F. CHAMPAYGNE SPECIMEN MOLDING 3 Sheets-Sheet 2 ATTORN EY June 20, 1950 E. F. CHAMPAYGNE SPECIMEN HOLDING 3 Sheets-Sheet ,3

Filed Feb. 3, 1945 Patented June 20, 1950 SPECIMEN MOLDING Edmund F. Champaygne, Noroton Heights, Conn., assigner to American Cyanamid Company, New York, N. Y., a corporation of Maine Application February 3, 1945, Serial No. 576,092

Claims. (Cl. 25051) The present invention relates to a method of forming a sample of polymorphic solid inorganic material used for a study of its transition characteristics through observation of the diffraction pattern formed when a collimating X-ray is projected therethrough. The invention further contemplates the formed sample per se, as well as the combination of such a sample and an X-ray camera for projecting a collimated X-ray tube therethrough.

ln the prior art it is customary to study high temperature transition ef such materials through study of their X-ray diffraction patterns and for this purpose what is known as a high temperature X-ray diiiraction camera is used. In such cameras means are provided for bringing the sample under study to the requisite temperature or temperatures at which transition takes place from one amorphic form to another. While ordinarily transmission of heat from the heating means to the sample undergoing study takes place through reflection and radiation, yet this may more efliciently be accomplished by means of conduction, and this specification discloses one such high temperature X-ray diffraction pattern camera where the sample undergoing study is heated through conduction.

It is to be understood that the present invention is applicable to any type of high temperature X-ray camera regardless of the method of heating the sample undergoing study, although numerous advantages occur when the specific camera of the present application is used with the sample here described.

In the formation of samples used in cameras of the above type it is important that the sample thickness measured along the axis of the X-ray beam projected therethrough be as small as possible. Unless this condition exists, a number of diffraction patterns will be projected onto the X-ray sensitive surface when a collimated X-ray beam is projected through the sample. It is an important object of the invention, therefore, to form and mount a sample in such a device which will have minimum thickness in the X-ray projected area s0 as to minimize interference with the'diiiraction pattern undergoing study.

Inasmuch as these samples are Aextremely small in the first place, and in the second place do not admit of binding agents to hold the various particles of the material undergoing study together, it is extremely difficult to cause the particles to stick together through coherence alone and still have thedesired thickness of the sample while at the same time sucient rigidity in the mount so as to preclude accidental displacement or'deformation of the sample during handling and study.

It is, therefore, another important object of the invention to provide a sample either formed initially in the sample holder of the camera or exteriorly thereof and then transferred into its final position in the sample holder, without breaking or distortion while at the same time maintaining desirable thickness.

The invention further includes the novel arrangement, combination and formation of the parts more fully hereinafter described and shown in the accompanying drawings, in which Fig. l is a side view showing the iilm cassette and its relation to the diffraction beam under study;

Fig. 2 is a section elevation of the collimating tube, sample holder and associated parts showing a preferred electrical hook-up;

Fig. 3 is an exploded perspective showing one method of assembly of the major parts of Fig. 2;

Fig. 4 is a perspective view of a sample holder;

Fig. 5 is a fragmentary sectional view on line 5-5 of Fig. 4 on an enlarged scale;

Fig. 6 is an exploded perspective view of the sample holder, plug and rod used in forming the sample undergoing study;

Fig. 7 is a fragmentary sectional view of a sample holder showing a sample being formed;

Fig. 8 is a similar vew showing the next step;

Fig. 9 is a similar view showing a formed sample; and

Fig. l0 is a similar view showing a modied sample.

Referring now with particularity to the embodiment illustrated, an X-ray collimating tube is shown at I, preferably of soapstone because of its reasonable heat resisting and insulating properties as well as its machinability. This tube is adapted to receive at the X-ray entry end the usual restrictor device 2 having a telescoping portion Y3 closely fitting the inside of the collimating tube and provided with a flange 4 abutting the end thereof. A lead or otherwise X-ray opaque shield 5 is located Within the inner periphery of the telescoping portion 3V and the face of the restricter 2 and the lead shield 5 are provided with primary and secondary restricting apertures 6 and 1, respectively. As is usual in devices of this character, the secondary aperture 1 is coaxial with the primary aperture 6 and slightly larger in diameter in order to transmit therethrough parallel X-rays entering the aperture B with minimum scattering.

rlhe open end of the collimating tube I is provided with a bell shaped extension 8 overlying the end portion 9 of a heat transmission barrel ii! preferably of stainless steel and provided with a terminal annular outwardly projecting flange II. As shown, the end 9 of the barrel Ill eX- tends telescopically within the bell II of the collimating tube .in a loose lit with an expansion element between the collimating tube and lthe heat transmission barrel which may conveniently take the form of a spring I2 of coiled nichrome wire or the like.

Barrel I is provided with a raised threaded portion I3 to receive the interiorly threaded ring I4, preferably of stainless steel or the .like which is secured as by machine screws I5 to an annular transite collar lli having .a projecting flange I1.

As shown, the inwardly projecting flange il .on the collar I6 abuts and engages the ilange Il on the `bell of the collimating tube l which also holds the end y9 vof the heat transmission barrel Ill against the expansion spring xI2 Aupon proper relative movement 4between the barre-l le and the threaded ring :I`4.

The main bodyof the barrel Ir may be wrapped 'with a layer .I9 of electrica-l insulation such' as mica or asbestos upon which :is wound :an 'electri- Acal resistance element `ill -o'f a size Vand extent suiicient to raise and maintain the sample at -a desired temperature, say up to '690 C. 'The Aends of the resistance` element '25 are connected through electrical 'leads 2l through Va variable voltage transformer 2.2 stepped down to about twenty-five volts, a .bleeder resistance element 23 for maintaining the temperature of the sample within close limits after the desired temperature has been reached, and an external` relay 24 to a potentiometer controller r2li to which fan E. M. F. from a .115 volt source is flowed by meansof leads 26 though `proper vmanipulation of switch '21.. Thus any idegreeof heat may be obtained, maintained, and adfrusted within the limit of the heating elements which'limit may conveniently lbe .approximate-ly 600 5C. Obviously, a device may 'be lconstructed Vto obtain higher or lower temperatures las' desired ley inerely changing the type of heating Ielement and/or the character vof the M. Esupplied thereto.

Insulation I253 is provided fior embedding the resistance wires 2-i1and to prevent :loss .of heat in a radial or :outward direction. This insulation may take the form of powdered or ia'ked asbestos although preferably it consists ci' a set packing of frebrick cement. In order to confine the insulation, transito washers 2l@ .and iii-il are provided, the latter being of .a :greater radial extent than `the former so `as to abut and hold vin place `an aluminum housing 3l held :between the washer 30 and the flange .I1 of the transita cellar Il. Thus the washer 2S :and the "housing 3l may serve as vforms `during the packing of the insulation material 28 after which the washer may be put in place. It is preferable that t -e Vinner `surface of "the aluminum housing 13! be polished or a supplemental reilector '.Bl'a l.provided so as to reflect any heat reaching -i-t from rthe inside 'back 'into the device.

A cylindrical restrictor 32, "preferably o stainless steel, having a restricting aperture 33 and engaged againstr an annular shoulder i3d machined on the vinside fof 'the barrel it is provided.

A metallic's'ample holder iis shown at 35 prei erably of stainless steel having Cylindrical portion 35 telescopically and closely engaging the inside oi" the barrel in good heat conduction contact therewith. As shown the end of the cylin drical portion 36 of the sample holder` abuts the guard 32 and holds the latter in xed position. The sample holder is also provided with an outwardly projecting flange 3l abutting the end of the barrel |10. The sample holder is also provided with an aperture 3S in which the sample undergoing study through its diiiraction pattern may be mounted. It is, of course, important that the apertures S, l, 33 and 38 be co-axial and arranged for the transmission therethrough of parallel X-ray beams from any suitable source not shown) An aluminum cap 39 having shoulder 48 is fitted over the end of the device so that the shoulder engages the edge portion of the washer 3l) and `an enlarged cylindrical portion 4I overlies the housing 3l in a close frictional t. The cap 39 is provided with a radial slot 42, the upper end of which is 4coincident with a horizontal line drawn outwardly from the upper inside surface of the sample receiving aperture 38, and the other .end of the slot is coincident with .a vertical line drawn downwardly and across the outer face 43 of the sample holder.

A thermocouple well Ml is provided in the sarnple holder as close to the sample receiving aperture 3,8 as possible and a thermocouple 45 is located therein and provided with leads 46 which pass through apertures in the transite washer t5 preferably through tube 41 embedded .in the insulation 28 and suitable 'apertures in the Washer 2S, .ring I4 and -.collar I6. These leads are then properly connected Ato the potentiometer controller asis usual in fsuch cases. As thus arranged t-he thermocoup-le and .its leads .may be readily removed for replacement or repair without disturbing the other Iparts with the exception of the removal Vof the aluminum cap 39.

In assembling the collimating tube and .the parts within the housing `3I and cap 3B, ythe following prooedure .may be used:

The 4collar I5 is slipped over the left-handsend of the collimating tube until the flanges cI'I and I I abut, the eXpansionspri-ng I2 is put in place, the barrel .Ill inserted and thering I4 lthreaded onto the barrel against the collar until the apertures through which the leads `24| of the resistance element 23 pass are .in.align-mentI .'I'he mach-ine screws I5 are -then putin place to secure the 'collar I5 .and the ring I4 together. Proper rotation of the barrel lil Awill then cause the iianges Il and II to be Vi-n close engagement aga-inst .the tension-of the sprl-ng I2. The washer is then slipped over the har-rel from the rig-htha-nd end thereof until it :abuts `thering I4 and the apertures :for the leads .2l of the `resistance 23ers in proper alignment. The mica or asbestos wrapping for the barrel is then put in placer and the resista-nce 20 assembled so that its leads 2l pass through the aligned :apertures in the vwasher ring I4 and colla-r 1.6. The .housing 3 I is then slipped over the washer 2.9 :and the .ring III so that its end abuts the flange I'I on the vcolla-1.' I The 4insulating packing 2S is .thenput v.place and closed by the -washer 38.

Following this operation the restrictor32 inserted inside of .the barrel Ill, the sample holder 35 containing :its prepared sample inserted :in :the end :of the .barreluntil the flange 310i the former engages the end \of the latter, the thermocouple 45 placed into lits well and its leads A6 :passed through the washer 3i), the tube 451 and the aligned Taperturesin washer'29, ring i4 and'collar' I 6 andproperly connected to the potentiometer controller 25. The aluminum cap 39 is then placed in position so that the slot 42 is in the proper location to permit projection of the diffraction pattern of the sample in the aperture 38 upon the iilm.

Fig. .1 shows the general relationship between the X-ray tube stack, the source of X-ray radiation, the sample holder, heater .and collimating tube assembly and the film cassette. In this iigure the stack is shown at 48 which is of conventional design housing a usual source of X-ray radiations which` are projected through the collimatlng tube l held in an annular hub 49 as by set screw 50. The hub is a part of the standard and well-known cylindrical lm cassette indicated generally at` which'is provided with the usual cylindrically arranged X-ray sensitive surface.

The assembly, including the aluminum housing 3l, is so arranged Within the lm cassette that a portion of the axis of the cassette lies in the plane of the outer face 43 of the sample holder, the parts being so positioned that the diiraetcd X-ray pattern projected through the slot 42 in the cap 39 extends through the Sil-degree arc 52 onto the lm in the cassette. As usual, the zero beam is caught Within a well 53 mounted on the cassette, the bottom of which is made of X-ray opaque material so as to provide minimum interference between the zero beam and theuseiul diracte'd beam to be studied.

Where the sample of material undergoing study and held in aperture 38 is subject to change due to oxidation or reduction, it may be desirable to maintain it in an atmosphere of either an inert, reducing or oxidizing gas as the case may be. In such cases, a gas inlet 54 in the wall of the collimating tube may be provided and a gas outlet 55 in the sample holder through which a gas ci any desired character may be passed.

In the investigation of polymorphic powder or crystals of inorganic materials through study ci their X-ray diraction patterns at high temperature, it is desirable that a sample be mounted in the sample holder in such a way as will insure the production of a sharp diffraction pattern brought about by the use of as thin a sample as possible. Two preferred modes of mounting a sample are shown in Figs. 9 and 10.

In one form, a plug 56 having axially projecting stud 51 is inserted inside of the sample holder 35 so that the stud projects within the sample receiving aperture 38 a desired distance. The top oi this stud may be flat as at 58 or it may be convex as at 59, dependent upon the desired shape to be given to the back side of the final specimen mounted in the aperture 38. Thus a mold cavity is formed in which the top of the stud 5'! is in ci fect a removable bottom of a mold cavity. 1n either event, a portion 60 of the material undergoing investigation is placed on the sample holder 35 in a quantity suficient to more than fill the remaining portion of the aperture 38 and smoothed off as by spatula El. while retaining the plug 56 and its stud 51 in place, a rod B2 having a knurled finger grip 63 and a convex end 54 is impressed into the loose powder 65 with oscillation so as to form a concavity 66 due to the curvature of the end 64. This then leaves the final Sample as shown in Fig. 9 upon remove? of the plug 56. It is desirable, of course, that the smallest thickness dimension of the sample be such that a sharp diffraction pattern may be obtained.

In order to render adequate strength to the bridged sample thus produced and to prevent its accidental displacement during handling incident to mounting in the complete device, it may be desirable to use a plug 56 having a stud with a convex face 59 thereon. Under these circumstances and manipulating the loose sample as before a bridged sample 68 is produced whichv is concave on each side. This type of bridged sample is stronger than the sample 61 as a supporting arch is formed on each side thereof.

Having thus :formed a sample, it only becomes necessary to insert the sample holder 35 into the end of the heat transmission barrel I0 of the assembly and proceed as before.

' In the above description it will be understood, of course, that where the sample is provided with only a single concave face, this concavlty may be either inside of the sample holder or on the outside, although the latter is perhaps more convenient.

Again it may be found desirable in some instances actually to form the sample in a dummy sample holder and after compacting and forming the sample into the desired shape with either one or two concave faces, to remove it from the dummy holder by removing the plug Y56 and pushing the thus-formed sample completely out of the aperture 38 as a unit.- This unit sample may then be transferred into the final sample holder, where it may be secured in place as by the usual cement, adhesive, or the like. In this Way a large number of samples may be prepared at one time extraneous of the camera and then transferred to the camera, Where they may be studied without tying up the camera or camera holder for long periods of time while additional samples are prepared directly in place in the latter.

A sample prepared as above has been found to be particularly sturdy and capable of reasonable handling without breaking or distortion.

It will be apparent that such samples may be used in any type of high temperature X-ray camera in which a collimated X-ray beam is projected through the sample and the diffraction pattern from the sample caught and recorded by an X-ray sensitive surface regardless of the particular construction of the camera itself or of the means used for getting the heat to the sample.

This application is related to applicants copending application Serial No. 576,091, now U. S. Patent 2,479,471.

While the invention has been described with particular reference to specific embodiments, it is to be understood that it is not to be limited thereto but is to be construed broadly and restricted solely by the scope of the appended claims.

What is claimed:

1. A method of forming a sample of polymorphic solid inorganic material for the study of its high temperature X-ray diffraction pattern which includes lling a mass of said material into a cylindrical apertures of the size and shape of that of the sample holder in which the sample will be held for study, compacting the material therein and forming an exposed concave surface in one face of the sample, the thickness dimension of the sample measured between the bottom of the concavity and its opposite face being such as to cause minimum X-ray diffraction interference when a collimated X-ray is projected therethrough.

2. A method of forming a sample of polymorphic solid inorganic material for the study 1o! :itshigh temperatureX-rayrdinractionpattern whichfincludes forming a mold -caviify by vplacing a removable surface Vin la cylindrical aperture, the diameter 1of which -is equal 'to that of anaper- 'ture in 1a sample :holder inwhich the sample :will lbe held for study, filling -a -mass of said material therein, compacting the material so that it will be lself -sustaining through cohesion, forming an vexposed concave surface in vone face of the sample, .the thickness dimension of -the sample measured between the :bottom of :the concavity and its opposite face being such as to cause minimum X-ray diiraction interference whena collimated X-iray is projected therethrough, and removing the removable sur-face from the zcylindrical aperture. i

v3. A `method lof Aforming a sample of polymorphic sol-id inorganic material for the study of its high temperature X-rayv-diifraction pat-tern which includes forming .a mold cavity by placing a removable convex surface in a cylindrical aperture, Ithe ,diameter of which is equal :to lthat of an aperture in `a -sample holder in which the sample will-be-heldior study, Vfilling amasscfsa-id ,material therein, com-pacting the material until it is `self-sustaining :th-rough cohesion, forming a second .concave surface in the sample, the thickness dimension ,of the `.sample measured between the bottoms .of the two kconcavities `being such as to .cause minimum X-ray diffraction interfer- Yence when `a ,collimated X-ray is projected therethrough and vremo-ving the removable convex suriace from the cylindrical aperture.

4. A sample of solid polymiirpl'iic @inorganic 4material prepared for lstudy fof :its iX-.raydiiraction pattern comprising a cohesive, compact mass of the material having cylindrical side walls and an exposed concave face, the thickness dimension of the sample measured between the 'bottom 'of the concavity and its opposite face `being such as to cause minimum X-ray diffraction linterference when a collimated X-ray is projected therethrough.

5. A sample of solid polymorphic inorganic material prepared for study of its X-ray diffraction pattern comprising a cohesive, 'compact mass of the material having cylindrical side Walls :and exposed opposite concave faces, the thickness dimension measured between `the bottoms of the concavities being such as to cause minimum X-ray diiraction interference when a collimated X-ray is projected therethrough.

EDMUND F. CHAlt/ifi?AYGNE.y

@ITER The following references are of record inthe e of this patent:

UNITED STATES .PATENTS lll McLachlan Apr. 20, 1943 

